Transition Metal Chemistry, 19 (1994) 75-77 Metal dihydrazino quinoxaline complexes 75

Structural elucidation of manganese(II), iron(III), cobalt(II),

nickel(II), copper(II) and zinc(II) complexes of a new multidentate
dihydrazino quinoxaline derivative
Dikonda S. Rani, Parupalli V. A. Lakshmi and Vuppalapati Jayatyagaraju*
Department of Chemistry, Osmania University, Hyderabad 500 007, India

Summary out on a microanalytical Perkin-Elmer 240C elemental

Manganese(II), iron(III), cobalt(II), nickel(II), copper(II) analyser. Chloride contents were estimated argentometri-
cally after igniting a definite weight of the complex in
and zinc(II) complexes of a new multidentate oxygen-
nitrogen donor, bis(N-salicylidene)-2,3-dihydrazino-l,4- oxygen in the presence of K O H and HzOz tv). For metal
estimations, the complexes were decomposed by slow
quinoxaline (HzBSDHQ) were prepared and characterised
by elemental analysis, conductance, thermal, spectral and evaporation of HC104 and H N O 3 solutions and the
resulting metal salts were dissolved in H 2 0 to give
magnetic data. H2BSDH Q deprotonates to give a dibasic
aqueous solutions of known dilution. The metal contents
O N N O donor set in a trivalent iron(III) complex, which
were estimated by the emission spectrophotometry tech-
binds to the divalent metal ions in a bis-tridentate fashion,
nique using a Lab tam plasma Scan-8410.
using two monobasic O N N donor sets, and resulting in
polymeric complexes. Octahedral geometries are proposed
for all these complexes, and preliminary studies show that Synthesis of H2BSDH Q
they possess potential antimicrobial activity. The H2BSDH Q ligand was prepared by a four step
process from the synthesis of quinoxaline-2,3-dione (QD) ~8~
Introduction and 2,3-dichloro quinoxaline (DQ) t9).
Quinoxalines are a class of fused six-membered heterocycles
2,3-Dihydrazino quino xaline ( QD H )
containing two nitrogens para to each other. Substituted
quinoxalines have featured widely in antimicrobial, M e O H (t 00 cm 3) was added to 2,3-dichloro quinoxaline
pharmacological, pesticidal, insecticidal and herbicidal (10 g), NzH4" H 2 0 (50 cm 3) and the mixture boiled under
studies "-4). The preparation of multidentate oxygen reflux in a steam bath for 8 h. The orange-yellow com-
nitrogen donor systems containing 1,4-quinoxaline and pound which separated was removed by filtration, washed
their metal complexes was undertaken to further investigate with small amounts of M e O H and dried in vacuo. Yield
their antimicrobial applications. This paper discusses the 65%; m.p. 240~ (dec) (found: C, 47.6; H, 5.2; N, 40.42,
synthesis and characterization of bis(N-salicylidene)-2,3- CaHx2N60 calcd: C, 46.15; H, 5.8; N, 40.4%). 1H n.m.r.
dihydrazino-l,4-quinoxaline (H2BSDHQ) (Figure 1) and (DMSO-d6): 6 11.0 (ring NH) (2), 6 6.8-7.5 (aromatic) (4),
its complexes with manganese(II), iron(III), cobalt(II), 65.4-5.8 (NH2) (4). Q D H - H 2 0 re~z=208. I.r. 3150-
nickel(II), copper(II) and zinc(II). 3300 c m - 1, v(NH2) (sym and asym); 1625 c m - 1 v(C=-N)
(exo) and v(C=C); 1600 cm-1 v(NH)(def) and v ( C = C )
Experimental and 1500cm- 1 v(C=N)(ring). U.v.-vis (VmaX in cm 1)
37174 (benzene ring), 26178 (ring NH), 24875 (azomethine),
Materials 23474 and 22075 ( N 2 H 4 chromophore).
AnalaR Grade metal chlorides were used as supplied. Bis(N-salic ylidene )-2,3-dih ydrazino-1,4-quinoxaline
Silicylaldehyde and NzH4"HzO were obtained from E.
Merck. Solvents were purified by established procedures (5). Salicylaldehyde (0.73 c m 3) w a s added to a solution of
2,3-dihydrazino quinoxaline (1.14g) in D M F (50cm3),
and the mixture boiled under reflux for 3 h. The mixture
Physical measurements and analysis was then poured into H 2 0 (150cm 3) and the pale green
Mass spectra were recorded on a Perkin-Elmer Hitachi compound which separated was removed by filtration,
RMU-6L spectrometer. 1H n.m.r, spectra were recorded on washed with a small amount of aqueous E t O H and dried
a Varian XL-200 MHz in DMSO-d 6. I.r. spectra (KBr in vacuo. Yield 70%; m.p. 142 ~ C. (Found: C, 64.85; H, 4.1;
discs) were recorded in the 4000-200 cm-~ region on a N, 20.9, C22HlsN602 calcd: C, 66.3; H, 4.5; N, 21.1%),
Perkin-Elmer 283-B. Reflectance spectra of solids were m/z = 398. 1H n.m.r. (DMSO-d6): 6 8.5 (azomethines CH)
recorded on a Cary-2390. Magnetic susceptibilities were (2), b 6.6 (NH) (2), 6 6.9-7.5 (aromatic) (12), 6 12.1 (OH) (2).
measured on a Faraday balance CAHN-7550-03, at room l.r. bands (cm-~): 3300-3000 br I v ( O H ) + v(NH)], 1620 s
temperature using HgCo(NCS)4 as the calibrant. Dia- v(C=N)(exo), 1540s, v(C~N)(ring), 1240s v(C O)
magnetic corrections using Pascal's constants and tem- (phenolic) and 1030 v(N--N). U.v.-vis. (Vm,x in cm-1):
perature-independent paramagnetic corrections were 37174 (ring rc ~ n* transition) and a multiple bond 25974-
computed (6). The electrical conductance measurements 21739 with components 25974, 25000, 22988 and 21739
were recorded using 10-3 molar solutions in D M S O with (~z--, g* and r/---,n* transitions). The data are consistent
an Elico conductivity bridge (Model CM-180) and a dip with the expected structure (Figure 1).
type cell calibrated with KC1 solutions.
Carbon, hydrogen and nitrogen analyses was carried Preparation of the complexes
The following general procedure was adopted. A M e O H
* Author to whom all correspondenceshould be directed. solution of the metal chloride (1 mol) was mixed with

0340-4285 9 1994Chapman& Hall

76 Rani et al. Transition Metal Chemistry, 19 (1994) 7 5 - 7 7

H complexes was established by d.t.a. E n d o t h e r m s indicate

N~N--N ~CH -- C6H4OH --O deaquation in a one step process for each complex in the
265-300 ~ C range.
N N -- N ~ CH -- C6H4OH -- O I.r. studies
H
The i.r. spectral data of the complexes are given in Table 1.
The manganese(II), cobalt(II), nickel(II), copper(II) and
Figure 1. Ligand structure: H2BSDHQ. zinc(II) complexes show changes in v ( C - - O ) , v ( C = N )
(ring) and v(C~-N)(exo), indicating binding to the metal
H 2 B S D H Q (1 mol). T o this a 5% M e O H solution of t h r o u g h an O N N sequence involving phenolic oxygen
a m m o n i a was added to maintain the reaction at p H 7, and
and azomethine nitrogens (x ~-~ 3). As these complexes are
the mixture was boiled under reflux in a steam bath for
isolated from neutral media, d e p r o t o n a t i o n of phenolic
3 h. The complex which precipitated was r e m o v e d by
oxygen has p r o b a b l y occurred. Indeed, the ~Hn.m.r.
filtration, washed with M e O H and dried in vacuo. The
spectrum of the zinc(II) complex confirms this fact (dis-
purities of H z B S D H Q and metal complexes were checked
appearance of the 6 12.1 signal). The u p w a r d v ( N - - N )
by t.l.c. The analytical data and p r o p o s e d formulae for the
shift in all the complexes in the 1 0 - 3 0 c m ~ range
complexes are given in Table 1.
supports involvement of one of the nitrogens in bonding ~14);
the iron(III) complex being the exception in v ( C = N )
Results and discussion (ring) ~'~ The b a n d at 2 9 0 0 - 3 4 0 0 c m - ~ in the iron(III)
The H 2 B S D H Q complexes are coloured and oxygen complex is assumed to be due to side chain v(OH) and
stable. They are insoluble in c o m m o n organic solvents but v(NH) ~s) and the m e d i u m intensity b a n d observed at
soluble in D M F and D M S O . They decompose at high 8 5 0 c m - ~ is assignable to the rocking m o d e (x6) of coor-
temperatures. Analytical data are c o m m e n s u r a t e with a dinated H 2 0 molecule. However, in the zinc(II) complex
1 : i metal to ligand stoichiometry in all complexes, except the b r o a d b a n d at 2 9 0 0 - 3 4 0 0 c m - i is a v(OH) and
in the zinc(II) complex (2:1). They have low m o l a r v(NH) c o m b i n a t i o n and shows the presence of H 2 0 and
conductances (f~M = 2.0-4.0 mhos m o l - 1 cm 2) in 1 x 10 3 ammonia ~ in c o o r d i n a t i o n sphere as established by
molar D M S O solutions at r o o m temperature and are M - - O H 2 and M--NH3(XT) rocking modes (850 and
therefore nonelectrolytes ~ m. The chloride in iron(III) and 910 c m - ~, respectively).
zinc(II) complexes lies within the c o o r d i n a t i o n sphere. The new bands in the far i.r. region (Table 1) are
The presence of coordinated H 2 0 in iron(III) zinc(II) attributed to v ( M - - O ) , v ( M - - N ) and v ( M - - C 1 ) (ls'19).

Table l. Analytical and i.r. data of the metal complexes of H2BSDHQ a'b.
Complex/ Found (calcd.)(%) v(NH) v((OH) +(NH)) v(C~N) v(C~N) v(C--O) v(N N) New bands
Stoichiometry M N (exo) (ring) (phenolic)
[MnUL] 12.55 18.5 3000-3300 - 1600 1520 1250 1260 1060 630, 490
(12.2) (18.6)
[FemLCI(H20)] 11.3 16.7 - 3000-3400 1600 1550 1240 1260 1040 850, 640, 385
(11,0) (16.6)
[ConL] 11.95 18.9 3000 3300 - 1600 1520 1240-1250 1040 620
(12.95) (18.5)
[NiUL] 13.1 18.4 3000-3300 - 1600 1520 1240-1250 1040 620
(12.9) (18.5)
[CunL] 14.1 18.7 3000, 3200, - 1600 1500 1230-1260 1040 640, 620
(13.8) (18.3) 3300
[Zn~L(NH3)z(H20)2Clz] 19.4 16.5 - 2900-3300 1600 1520 1240-1260 1050 910, 850, 630,
(19.6) (16.77) 610, 300
aAll i.r. bands in cm- 1; babbreviation: H2BSDHQ = bis(N-Salicylidene)-2,3-dihydrazino- 1,4-quinoxaline (C22H 18N602), L = C22H1 6 N 6 0 2 '

Table 2. Magnetic moment and electronic spectral data of metal-H2BSDHQ complexest

Complex ~eff (B.M.) Vmax Assignment

(temperature in K) (cm-1)

[MnIIL] 5.85 25316, 23255, 22222, -

(295) 19607, 17543, 15625,
15151, 13888, 12987
[FemLCI(H20)] 6.06 25641, 22727, 21737,
(295) 16393, 15625, 14925,
13888, 12820
[foUL] 3.95 25000-20000 4 Z i g --4 4Tlg(p )
(295)
[-NinL] 3.03 23255 3A20 ~ 3Tla(P )
(295) 17543 3A2 --~3T1
10869 3A g __+3T g
~2g 20 *

16393-15151 SA2_-* 1E_

[CuIIL] 1.73 18181 2Bf---~ZE"
(295) 17241 2 B Ig~ 2 Bz.
g
15625 2Big ~ 2Alg

"HeBSDHQ = bis(N-salieylidene)-2,3-dihydrazino-l,4-quinoxaline (C22HlsN602) , L = C22H16N602.

 Transition Metal Chemistry, 19 (1994) 75-77 Metal dihydrazino quinoxaline complexes 77

azomethine chromophore-metal binding. The broad bands

in this range may also have d - d component transitions
corresponding to the complexed transition metal ions.
The electronic spectra of manganese(II) and iron(III)
exhibit several weak absorptions due to doubly forbidden
N'N"U N''- N. d - d transitions (2~). As such, no specific assignments for
the electronic transition could be made, The nephalauxetic
and inter electron repulsion parameters for the nickel(II)
complex are B = 546.06 and fl = 0.524, which indicate a
strong ligand field around the metal ion. The analytical,
conductivity, thermal and spectral characteristics correlate
to suggest a bis-tridentate mode towards divalent metal
ions and a tetradentate mode towards iron(Ill). The
dependence of this binding mode on charge is interesting.
U = Un II, CuI], NiH, CoH In manganese(II), cobalt(II), nickel(lI) and copper(II)
complexes these interactions can be justified in terms of
(2) polymers and the proposed structures of complexes are
Figure 2. H z B S D H Q - M n u, - C o u, - N i n and - C u H complexes. given in Figures 2-4.
Preliminary studies on the bactericidal properties of
H z B S D H Q , its metal complexes, QD, DQ, Q D H and
related compounds, indicate promising activity against
Staphylococcus Aureus and Escherichia Colt. Detailed
studies are in progress.
N N
Acknowledgements
HN NH One of the authors (P. V. A. L.) thanks the CSIR, India,
\ Cl I for the Senior Research Fellowship.
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This result may be attributed" to the changes in the
electronic environment of the ligand as a consequence of (Received 20 January 1993) T M C 2957